Sulfonamide wax emulsions



Patented May 2, 1950 SULFONAMIDE WAX EMULSIONS David Aelony, Minneapolis, Minn., assignor to General Mills, Inc., a corporation of Delaware No Drawing. Application February 24, 1948, Serial No. 1|,553

7 Claims. (Cl. 106-287) 1 The present invention relates to sulfonamide wax emulsions and to a method of preparing them.

Wax emulsions commonly in use today generally contain carnauba wax. These compositions are composed of oil-in-water type emulsions containing some anionic emulsifying agent. It is important that the emulsion be of the oil-inwater type inasmuch as in this form it is possible for the emulsion to be thinned by the addition of further quantities of water. When these emulsions are in the reverse form, namely a water-inoil type, they form gels which cannot be thinned with water inasmuch as the gels merely absorb further quantities of water. It has been found that emulsions of carnauba wax prepared with cationic emulsifying agents such as octadecyl trimethyl ammonium chloride, formed water-in-oil type emulsionswhich gelled on standing, thereby rendering them unsuitable for use as emulsions.

In preparing emulsions of wax of the type herein described, such as N,N-dihydroxyethyl p-toluene sulfonamide distearate, it was found that the emulsions prepared with anionic emulsifying agents gelled on standing for relatively short periods of time. Such compositions were useless where the employment of an emulsion was desirable. This was found to be true after numerous attempts with a wide variety of anionic emulsifying agents.

It has now been found that excellent emulsions of sulfonamide ester waxes of p the type above mentioned can be prepared by the use of cationic emulsifying agents. Some of these have been in storage for more than eight months and have exhibited no tendency toward thickening.

It is, therefore, an object of the present invention to provide oil-in-water emulsions of aryl sulfonamide ester waxes of the above type employing cationic emulsifying agents, which emulsions do not have a tendency to gel upon standing for extended periods of time.

The waxes which may be employed in the present invention are N,N-dihydroxyethyl aryl sulfonamide diesters of higher fatty acids, preferably saturated higher fatty acids. Typical of these waxes are the higher saturated fatty acid esters of N,N-dihydroxyethyl benzene sulfonamide, N,N-dihydroxyethyl p-toluene sulfonamide, N,N-dihydroxyethyl p-chlorbenzene sulfonamide, and the like. Of the esters, the stearates are preferred inasmuch as these are waxes of high melting point. For esterification commercial stearic acid may be employed or any mixed steal-1c acid containing not more than about unsaturated acids. It is also possible to produce desirable waxes from other saturated fatty acids such as palmitic acid or from any saturated acid containing 12 or more, carbon atoms. These waxes may be prepared in accordance with the teaching of my copending application, Serial No. 643,748, filed January26, 1946 (now Patent No. 2,496,650), entitled Esters of hydroxyalkyl aromatic sulfonamides.

The cationic emulsifying agents may be of various types. It is preferred to employ quaternary ammonium salts having the following general formula:

BALM- in which R is a long chain aliphatic group containing from 12-24 carbon atoms, and R ll. and B may represent alike or diflerent low aliphatic groups, such as methyl, ethyl, etc. Similar com pounds in which the nitrogen has attached to it the residue ofa pyridine ring in place of the groups R R and ll. may be used. Typical of the cationic emulsifying agents which are suitable for this purpose is octadecyl trimethyl ammonium chloride. Numerous other compounds of this type which meet the above formula may be used for this purpose. Other cationic emulsifying agents which are suitable include 1-hydroxyethyl-2-heptadeceny1 glyoxalldlne.

The following examples will serve to illustrate the invention:

1 Example 1 210 g. diethanolamine were dissolved in 700 cc.

water and the mixture was heated to C. 190.5 g. p-toluene sulfonchloride were added at once. A violent reaction accompanied by boiling took place, and a homogeneous solution resulted. On cooling, .2. dark lower layer separated which solidified at 45 C. It was filtered and recrystallized from methanol yielding 156 g. white crystals M. P. 101.5-103.5 C. and 42 g. white powder (from mother liquor) M. P. 97.5- G. The total yield was 76.5 theory.

129.5 g. N,N-di-beta-hydroxyethyl p-toluene sulfonamide, 280.5 g. of a commercial stearic acid (Neo Fat 1-65) l g. p-toluene sulfonic acid monohydrate and 250 cc. xylene were refluxed over a Stark and Dean tube for two hours. A total of 18 cc. of water was collected in the trap. The prodnot was poured into 1.5 liters butanol, was allowed to stand overnight and filtered. After flve days of air drying 353.5 g. of the product (92% yield) M. P. 68.569.5 C. were obtained. Percent N found 1.765 (theory for the stearate, 1.78) acid number 2.4. When melted and allowed to solidify a beautiful hard shiny solid is formed (penetration in 30 sec. with a 200 g. load, ASTM needle, was 3, while it was 1 for carnauba No. 1).

3 g. of octadecyl trimethyl ammonium chloride were dissolved in 183 cc. of boiling water and agitated with 14 g. of N,N-dihydrxyethyl ptoluene sulfonamide distearate. The mixture was put through a hand homogenizer twice and was then allowed to cool. Upon storage for eight months the emulsion showed no sign of thickening.

Example 2 A wax emulsion was prepared in exactly the same manner as Example 1, employing N,N-dihydroxyethyl benzene sulfonamide distearate. The product was found to be a desirable wax emulsion.

Example 3 A wax emulsion was prepared in exactly the same manner as Example 1, except that N,N-dihydroxyethyl p-chlorbenzene sulfonamide distearate was employed. The product obtained was a desirable Wax emulsion.

Example 4 A wax emulsion was prepared in exactly the same manner as Example 1, except that l-hydroxyethyl-2-heptadecenyl glyoxalidine was employed. The product obtained was a desirable wax emulsion.

In contrast to these examples, numerous examples were performed employing anionic emulsifying agents, and it was found that they either did not emulsify the wax at all, or emulsified it very poorly, or formed a gel. All such compositions were unsuitable for the purpose for which a wax emulsion is intended.

It will be apparent, therefore, that the emulsion compositions of the present invention are stable oil-in-water emulsions of novel wax compositions and render them suitable for use in this form.

While various modifications of the invention have been described, it will be apparent that others are possible without departing from the spirit of the invention. Thus it will be apparent that numerous wax compounds coming within applicant's general formula may be employed.

portions. It is likewise apparent that addltimal materials may be included in the composition. It is to be understood, therefore, that the invention is not limited to such specific embodiments. but may be varied within the scope of the following claims.

I claim as my invention:

1. An oil-,in-water emulsion of a synthetic wax comprising N,N-dihydroxyethyl aryl sulfonamide diester of a higher fatty acid, said emulsion containing a cationic emulsifying agent.

2. An oil-inwater emulsion of a synthetic wax comprising NN-dihydroxyethyl aryl sulfonamide diester of a higher fatty acid, said emulsion containing a cationic emulsifying agent having the following formula in which R is a long chain aliphatic radical containing from 12-24 carbon atoms, and R, R and R represent low aliphatic radicals.

3. An oil-in-water emulsion of a synthetic wax comprising N,N-dihydroxyethyl aryl sulfonamide diester of a higher fatty acid, said emulsion containing octadecyl trimethyl ammonium chloride.

4. An oil-in-water emulsion of a synthetic wax comprising N,N-dihydroxyethyl aryl sulfonamide distearate, said emulsion containing a cationic emulsifying agent.

5. An oil-in-water emulsion of a synthetic wax comprising N,N-dihydroxyethyl benzene sulfonamide distearate, said emulsion containing octadecyl trimethyl ammonium chloride.

6. An oil-in-water emulsion of a synthetic wax comprising N,N-dihydroxyethyl p-toluene sulfonamide distearate, said emulsion containing octadecyl trimethyl ammonium chloride.

7. An oil-in-water emulsion of a synthetic wax comprising N,N-dihydroxymethyl p-chlorbenzene sulfonamide distearate, said emulsion containing octadecyl trimethyl ammonium chloride.

DAVID AELONY.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS 

1. AN OIL-IN-WATER EMULSION OF A SYNTHETIC WAX COMPRISING N,N-DIHYDROXYETHYL ARYL SULFONAMIDE DIESTER OF A HIGHER FATTY ACID, SAID EMULSION CONTAINING A CATIONIC EMULSIFYING AGENT. 